AU2007337982A1 - Reinforcing system for reinforcing a cavity of a structural element - Google Patents

Description

WO 2008/077944 PCT/EP2007/064464 Reinforcing system for reinforcing a cavity of a structural element Field of the Invention 5 The invention is based on a reinforcing system for reinforcing a cavity of a structural element in accordance with preamble clause of the first claim. The invention is likewise based on a method of 10 reinforcing a cavity of a structural element in accordance with preamble clause of the independent method claim. Description of the Prior Art 15 Structural elements frequently have cavities, particularly in order to permit lightweight constructions. These cavities, however, give rise to a wide variety of problems. Depending on the nature of 20 the cavity, it has to be sealed off in order to prevent penetration of moisture and dirt that can lead to the corrosion of the structural elements. Often it is also desirable to provide the cavities and hence the structural element with substantial reinforcement, but 25 while retaining the light weight. Often it is also necessary to stabilize the cavities and hence the structural elements in order to reduce noise, which would otherwise be transmitted along or through the cavity. Many of these cavities have an irregular shape 30 or narrow dimensions, thereby making it more difficult to provide them with correct sealing, reinforcement, and damping. Particularly in order to enhance the mechanical 35 characteristics of vehicle structures, also referred to below as bodywork, such as, for example, the crash performance, the stiffness, improved vibration damping, and so on, it is known to install local reinforcing WO 2008/077944 PCT/EP2007/064464 -2 structures into the vehicle structure. These local reinforcing structures consist, for example, of metal such as aluminum or steel, plastic, structural foams or combinations of these materials. These reinforcing 5 structures are positioned in the vehicle structure and connected to it. Metallic reinforcing structures can be connected to the vehicle structure by means, for example, of welding, but this is not always possible and does not always allow effective reinforcement. 10 Connecting by means of a structural foam as well does not always produce the desired results. A first reason for this is that the layer of structural foam is relatively thick, and a second is that the mechanical properties of these structural foams are moderate, 15 particularly in relation to the shear strength, the adhesion, and the unsatisfactory behavior at high temperatures. Summary of the Invention 20 The invention is based on the object of avoiding the disadvantages of the prior art in a reinforcing system of the type specified at the outset, and of providing an improved reinforcing system. 25 In accordance with the invention this is achieved through the features of the first claim. The core of the invention, therefore, is that the 30 support element has channels, that an adhesive is disposed in the cavity between the support element and the structural element, and that the adhesive can be introduced into the cavity between the support element and the structural element by means of the channels. 35 The advantages of the invention are to be seen in the facts, among others, that WO 2008/077944 PCT/EP2007/064464 -3 the subsequently injected adhesive can be adapted arbitrarily to the desired conditions in the process of producing the structural element. A reinforcing system of this kind therefore has much better properties than 5 existing systems with foamable materials. Thus, for example, the desired mechanical properties can be selected specifically, something which is only a limited possibility in the case of foamable materials. In addition, the properties at high temperatures can be 10 set much more effectively with a subsequently injected adhesive. Moreover, there are no ageing problems and there is no loss of properties in the course of transit, storage or installation. Moreover, the system shown here is outstandingly suitable for repair 15 solutions which, additionally, have the same properties as the originally installed parts. Furthermore, it is also possible for an existing carrier element to have adhesive introduced subsequently, which means that parts which possibly are not holding properly can be 20 fixed anew. Further advantageous embodiments of the invention are apparent from the dependent claims. 25 Brief Description of the Drawing Working examples of the invention are elucidated in more detail below with reference to the drawings. Equal or equivalent elements in the various figures are given 30 the same reference symbols. The direction of flow of the media is indicated by arrows. Fig. 1 shows a cross section through a prior-art reinforcing element; 35 fig. 2A shows a cross section through an inventive reinforcing element; fig. 2B shows a cross section through a further inventive reinforcing element; WO 2008/077944 PCT/EP2007/064464 -4 fig. 2C shows a cross section through a further inventive reinforcing element; fig. 3A shows a plan view of an inventive reinforcing element; 5 fig. 3B shows a plan view of the inventive reinforcing element from fig. 3A, with depiction of the internal channels; fig. 4 shows a plan view of a further inventive reinforcing element; 10 fig. 5 shows a diagrammatic representation of the adhesive fill operation. Only those elements that are essential for the immediate understanding of the invention have been 15 shown. Description of the Preferred Embodiment Fig. 1 shows a known reinforcing element 20. It is 20 disposed in a cavity of a body 21 of a vehicle, in this case a column of the bodywork. It is self-evident that a reinforcing element of this kind may be disposed in any cavity of the bodywork. The reinforcing element 20 comprises a carrier element 22 and a part 23 comprising 25 a foamable material. Foamable materials of this kind foam preferably under the influence of heat. A preferred thermally foamable material is sold, for example, under the brand name SikaBaffle@ 240, or 250 or 255, and is described in US patents 5,266,133 and 30 5, 373,027, whose disclosure is hereby incorporated. Alternatively, the thermally expanding material may also have reinforcing properties; material of this kind is sold, for example, under the brand name SikaReinforcer@ 941, and is described in US patent 35 6,387,470, whose disclosure is hereby incorporated. It is of course also possible to use other foamable materials, which may possibly be activated by external heat sources or internal heat sources, such as by an WO 2008/077944 PCT/EP2007/064464 -5 exothermic reaction, for example. The reinforcing element 20 is fixed in the cavity of the bodywork, typically by means of a fixing element, but may also be fixed in other ways. The carrier element 22 is composed 5 typically of polyamide, but may also be made of other materials or material components, including, more particularly, of metal. In its unfoamed state the foamable material has a 10 thickness 24 and a distance 25 from the bodywork. This distance 25 is necessary to allow the bodywork to be coated in the deposition bath and in order to have sufficient tolerance for the installation of the reinforcing part 20. After foaming has taken place, the 15 foamed material fills out the entire cavity and at this point has a thickness 26 which corresponds to the thickness 24 of the unfoamed material plus the distance 25 from the bodywork; the thickness 26 is typically approximately 6 to 10 mm. This relatively high 20 thickness 26 and the structural foam give rise to the disadvantages of the systems used to date. Figures 2A, 2B, and 2C now show inventive reinforcing elements 1. Each reinforcing element 1 comprises a 25 carrier element 2. The distance 3 between carrier element 2 and bodywork 21 is much lower here in comparison to the distance 26 from figure 1. The distance 3 can in this case be reduced to the distance necessary in order to allow the bodywork to be coated 30 in the deposition bath and to have sufficient tolerance for the installation of the reinforcing part 1; typically this is about 3 to 5 mm. Since it is possible through the carrier element to dispose channels for coating in the deposition bath, the distance 3 can in 35 fact be reduced still further to the tolerance that is needed for installation, increased by 1 to 2 mm as needed for the binding material, hence allowing the WO 2008/077944 PCT/EP2007/064464 -6 overall distance to be reduced to approximately 2 to 4 mm. The carrier element 2 is then connected to the bodywork with an adhesive 4. This adhesive 4 is injected 5 subsequently after the carrier element 2 has been installed, and for this purpose the carrier element may have special internal channels 5, e.g., tubular, or external channels 6, or - not shown - a combination of internal and external channels. The subsequently 10 injected adhesive may be adapted to the desired conditions and therefore has much better properties than existing foamable materials. Thus, for example, the desired mechanical properties can be selected specifically, something which is only of limited 15 possibility in the case of foamable materials. In addition, the properties at high temperatures can be set very much more effectively with a subsequently injected adhesive. Moreover, there are no ageing problems and there is no loss of properties in the 20 course of transit, storage or installation. Moreover, the system shown here is outstandingly suitable for repair solutions which, additionally, have the same properties as the originally installed parts. In the case of an existing carrier element, moreover, it is 25 also possible for adhesive to be introduced subsequently, and so parts which possibly are not holding correctly can be fixed anew. The carrier element may be made of any desired 30 materials, as for example of a plastic such as polyurethane foam, which may be reinforced with fibers or beads, of polyamide, etc., or of metal such as aluminum, foamed aluminum, steel, etc., or a combination of these materials. 35 There are a very wide variety of systems that can be employed for the reactive adhesive. An essential point of the present invention, however, is that the reactive WO 2008/077944 PCT/EP2007/064464 -7 adhesive, in accordance with the temperatures which occur subsequently in the operation, can be selected such that sufficiently quick curing takes place to give the desired mechanical properties. If, for example, the 5 part passes through a standard paint drying oven at temperatures of 165-180 0 C for about 30 minutes, then typical structural 1K [one-component] epoxide-based structural adhesives can be used. In the case of lower curing temperatures it is preferred to use two 10 component systems. Through the present invention it is possible in each case to select adhesives which correspond precisely to the conditions desired by the manufacturer. If, for example, the manufacturer wishes to install the reinforcing parts at room temperature, 15 this is possible with no problems. It is also possible to adapt the nature of the adhesive immediately to altered on-site production conditions without changing the carrier element. If, for example, the reinforcing part is now to be installed at higher temperatures, in 20 order, for example, to simplify the production operation, an adhesive is simply used which cures at the corresponding temperature. Table 1 compares typical data for a conventionally used 25 foam with those of an adhesive for use in accordance with the invention. These data represent only preferred ranges and it is of course also possible to use adhesives having other properties. The adhesives to be used in accordance with the invention may of course 30 also be filled, as for example with reinforcing materials such as fibers. In order to prevent contraction and stresses on curing, the adhesive of the invention preferably has a volume expansion of 0 to 10%, more particularly 0 to 5%. 35 Conventional Adhesive of foam the invention Expansion 40%-200% 0-5% WO 2008/077944 PCT/EP2007/064464 -8 Compression modulus 200-750 MPa 1000-4000 MPa Max compressive stress 5-20 MPa Tension modulus 400-1500 MPa 1000-4000 MPa Max tensile stress 2-10 Mpa 20-50 MPa Max shear stress 2-8 Mpa 15-30 MPa Table 1 Shown below are reactive adhesives which can be used for the invention. It is of course also possible for 5 other adhesives to be employed, if they have the requisite properties. Examples of reactive adhesives: One-component systems 10 A one-component reactive adhesive which can be used for the invention is a storage-stable polymer composition which is characterized in that it comprises at least one resin A that enters into polymerization reactions, at least one curing agent B, more particularly a 15 blocked curing agent, at least one additive D, and also, optionally, further components, with preferably at least one of the components A or B being present in a blocked form. 20 In a first embodiment the one-component reactive adhesive is a polyurethane composition. It is characterized in that it comprises a polyurethane polymer containing free or blocked isocyanate groups as the resin A that enters into polymerization reactions. 25 The term "polymer" refers in the present document on the one hand to a collective of macromolecules which, while being chemically uniform, nevertheless differ in respect of degree of polymerization, molar mass, and chain length, and that has been prepared by means of a 30 polymerization reaction (addition polymerization, polyaddition or polycondensation). On the other hand the term "polymer" in this document also encompasses derivatives of such a collective of macromolecules from WO 2008/077944 PCT/EP2007/064464 -9 polymerization reactions - in other words, compounds which have been obtained by reactions, such as additions or substitutions, for example, of functional groups on existing macromolecules, and which may be 5 chemically uniform or chemically nonuniform. The term "polymer composition" refers in the present document to a homogeneous or heterogeneous mixture of substances which is composed of one or more polymers or which comprises polymers to a substantial degree. 10 The term "polyurethane" in the present document encompasses all polymers which are prepared by the diisocyanate polyaddition process. This also includes those polymers which are virtually or entirely free from urethane groups, such as polyether-polyurethanes, 15 polyester-polyurethanes, polyether-polyureas, polyureas, polyester-polyureas, polyisocyanurates, polycarbodiimides, etc. The prefix "poly" in substance names such as "polyol", "polyisocyanate" or "polyamine" refers in the present 20 document to the fact that the substance in question contains formally more than one per molecule of the functional group that occurs in its name. The polyurethane polymer containing isocyanate groups 25 is prepared by reacting at least one polyol with at least one polyisocyanate. This reaction may be accomplished by reacting the polyol and the polyisocyanate by typical methods, as for example at temperatures of 500C to 100 0 C, where appropriate with 30 accompanying use of suitable catalysts, the polyisocyanate being metered in such a way that its isocyanate groups are present in a stoichiometric excess in relation to the hydroxyl groups of the polyol. The excess of polyisocyanate is selected such 35 that in the resulting polyurethane polymer, after the reaction of all of the hydroxyl groups of the polyol, there remains, for example, a free isocyanate group content of 0.1% to 15% by weight, preferably 0.5% to 5% WO 2008/077944 PCT/EP2007/064464 - 10 by weight, based on the overall polyurethane polymer. Where appropriate the polyurethane polymer can be prepared with the accompanying use of plasticizers, in which case the plasticizers used contain no isocyanate 5 reactive groups. As polyols for preparing a polyurethane polymer of this kind containing isocyanate groups it is possible to make use for example of the following commercial polyols or any desired mixtures thereof: 10 - Polyoxyalkylene polyols, also called polyether polyols, which are polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide, tetrahydrofuran or mixtures thereof, optionally polymerized by means of a starter molecule having two 15 or more active hydrogen atoms such as, for example, water, ammonia or compounds having two or more OH or NH groups such as, for example, 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols 20 and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1,3- and 1,4 cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1,1,1-trimethylolethane, 1,1,1 25 trimethylolpropane, glycerol, aniline, and mixtures of the aforementioned compounds. Use may be made not only of polyoxyalkylene polyols which have a low degree of unsaturation (measured in accordance with ASTM D-2849 69 and expressed in milliequivalents of unsaturation 30 per gram of polyol (meq/g)), prepared for example with the aid of what are known as double metal cyanide complex catalysts (DMC catalysts), but also of polyoxyalkylene polyols having a high degree of unsaturation, prepared for example with the aid of 35 anionic catalysts such as NaOH, KOH or alkali metal alkoxides.

WO 2008/077944 PCT/EP2007/064464 - 11 Particular suitability is possessed by polyoxyalkylene diols or polyoxyalkylene triols, especially polyoxypropylene diols or polyoxypropylene triols. Especially suitable are polyoxyalkylene diols or 5 polyoxyalkylene triols having a degree of unsaturation of less than 0.02 meq/g and having a molecular weight in the range from 1000 to 30 000 g/mol, and also polyoxypropylene diols and trials having a molecular weight of 400 to 8000 g/mol. By "molecular weight" or 10 "molar weight" is always meant in the present document the molecular weight average M,. Likewise particularly suitable are what are called "EO-endcapped" (ethylene oxide-endcapped) polyoxypropylene diols or trials. The latter are 15 special polyoxypropylene-polyoxyethylene polyols which are obtained, for example, by alkoxylating pure polyoxypropylene polyols with ethylene oxide after the end of the polypropoxylation, and which consequently contain primary hydroxyl groups. 20 - Styrene-acrylonitrile-grafted polyether polyols, of the kind supplied, for example, by Bayer under the name Lupranol. - Polyester polyols prepared, for example, from dihydric to trihydric alcohols such as, for example, 25 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol, glycerol, 1,1,1 trimethylolpropane or mixtures of the aforementioned alcohols with organic dicarboxylic acids or their 30 anhydrides or esters such as, for example, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid and hexahydrophthalic acid or mixtures of the 35 aforementioned acids, and also polyester polyols from lactones such as E-caprolactone, for example. - Polycarbonate polyols of the kind obtainable by reaction, for example, of the abovementioned alcohols - WO 2008/077944 PCT/EP2007/064464 - 12 those used to construct the polyester polyols - with dialkyl carbonates, diaryl carbonates or phosgene. - Polyacrylate and polymethacrylate polyols. - Polyhydroxy-terminated polybutadiene polyols, such 5 as, for example, those prepared by polymerizing 1,3 butadiene and allyl alcohol. - Polyhydroxy-terminated acrylonitrile/polybutadiene copolymers, of the kind preparable, for example, from epoxides or amino alcohols and carboxyl-terminated 10 acrylonitrile/polybutadiene copolymers (available commercially under the name Hycar@ CTBN from Hanse Chemie). These stated polyols have an average molecular weight of 250 to 30 000 g/mol, more particularly of 1000 to 30 000 g/mol, and an average OH functionality 15 in the range from 1.6 to 3. Further to these stated polyols it is possible for low molecular mass dihydric or polyhydric alcohols such as, for example, 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene 20 glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1,3- and 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, 25 dimeric fatty alcohols, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol, pentaerythritol, sugar alcohols and other high-functionality alcohols, low molecular mass alkoxylation products of the aforementioned dihydric and polyhydric alcohols, and 30 also mixtures of the aforementioned alcohols to bemused accompanyingly when preparing the polyurethane polymer. Polyisocyanates used for preparing a polyurethane polymer of this kind containing isocyanate groups are commercial polyisocyanates. Examples include the 35 following polyisocyanates which are very well known within polyurethane chemistry: 2,4- and 2,6-Tolylene diisocyanate (TDI) and any desired mixtures of these isomers, 4,4'-diphenylmethane WO 2008/077944 PCT/EP2007/064464 - 13 diisocyanate (MDI), the positionally isomeric diphenylmethane diisocyanates, 1,3- and 1,4-phenylene diisocyanate, 2 ,3,5,6-tetramethyl-1,4-diisocyanato benzene, 1,6-hexamethylene diisocyanate (HDI), 5 2 -methylpentamethylene-1,5-diisocyanate, 2,2,4- and 2,4,4-trimethyl-1,6-hexamethylene diisocyanate (TMDI), 1,12-dodecamethylene diisocyanate, cyclohexane 1,3- and 1,4-diisocyanate and any desired mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanato 10 methylcyclohexane (isophorone diisocyanate or IPDI), perhydro-2,4'- and -4,4'-diphenylmethane diisocyanate (HMDI), 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), m- and p-xylylene diisocyanate (XDI), 1,3- and 1,4-tetramethylxylylene diisocyanate (TMXDI), 1,3- and 15 1,4-bis(isocyanatomethyl)cyclohexane, and also oligomers and polymers of the aforementioned isocyanates, and also any desired mixtures of the aforementioned isocyanates. Particular preference is given to MDI, TDI, HDI and IPDI, and also mixtures 20 thereof. The most preferred are MDI and TDI and their mixtures. In one preferred embodiment the polyurethane polymer containing isocyanate groups is blocked. This blocking is accomplished by the reaction of the polyurethane 25 polymer containing isocyanate groups with a blocking agent. This reaction takes place preferably by adding the blocking agent to the polyurethane polymer containing isocyanate groups in a stoichiometric ratio, based on the isocyanate group content, and reacting 30 this system at a temperature of 20 to 120 0 C until there are virtually no free isocyanate groups detectable any longer. If desired it is possible to use a catalyst also, such as a tin compound or a bismuth compound, for example. Examples of suitable blocking agents are 35 phenols such as phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, p-tert-butylphenol, p-tert octylphenol, nonylphenol, dodecylphenol, thymol, p naphthol, p-nitrophenol, p-chlorophenol, 2-pyridinol; WO 2008/077944 PCT/EP2007/064464 - 14 hydrocarbon resins containing phenol groups, such as cumarone-indene resins, petroleum resins, terpene resins; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, 2-butanol, isobutanol, ethylene 5 glycol, ethylene glycol methyl ether (Methyl Cellosolve@), ethylene glycol butyl ether (Butyl Cellosolve@), ethylene glycol phenyl ether (Phenyl Cellosolve@), diethylene glycol monomethyl ether (Methyl-Carbitol@), diethylene glycol monobutyl ether 10 (Butyl-Carbitol@), benzyl alcohol, furfuryl alcohol, cyclohexanol; 1,3-dicarbonyl compounds such as dimethyl malonate, diethyl malonate, diethyl methylmalonate, ethyl acetoacetate, 2,4-pentanedione; mercaptans such as butyl mercaptan, hexyl mercaptan, dodecyl mercaptan, 15 thiophenol, 2-mercaptopyridine; carboxamides such as acetamide, acetanilide, acetaniside, benzamide; carboximides such as succinimide, maleimide; amines such as diisopropylamine, dicyclohexylamine, N-tert butyl-N-benzylamine, 2,6-dimethylpiperidine, diphenyl 20 amine, phenylnaphthylamine, aniline, 9H-carbazole; nitrogen heterocycles such as imidazole, 2-methyl imidazole, 2-ethylimidazole, benzimidazole, pyrazole, 3,5-dimethylpyrazole, 1,2,4-triazole, benzotriazole; ureas such as urea, thiourea, imidazolidin-2-one; 25 aldoximes such as formaldoxime, acetaldoxime; ketoximes such as methyl ethyl ketoxime, methyl isopropyl ketoxime, methyl isobutyl ketoxime, methyl amyl ketoxime, diisopropyl ketoxime, cyclohexanone oxime; lactams such as £-caprolactam, 6-valerolactam, 30 y-butyrolactam, P-propiolactam; imines such as ethyleneimine; N-hydroxysuccinimide; 2-benzoxazolone; 1,3-benzoazine-2,4-dione; bisulfites such as sodium bisulfite, potassium bisulfite; and further blocking agents, as set out in the two review articles by 35 D.A. Wicks and Z.W. Wicks, Jr., "Blocked Isocyanates", which appeared in Progress in Organic Coatings 36 (1999), 148-172 and Progress in Organic Coatings 41 (2001), 1-83. Preferred blocking agents are phenols, WO 2008/077944 PCT/EP2007/064464 - 15 hydrocarbon resins, alcohols, oximes, nitrogen heterocycles, 1,3-dicarbonyl compounds, amines, and lactams. Particularly preferred are methyl ethyl ketoxime, methyl isobutyl ketoxime, pyrazole, 5 3,5-dimethylpyrazole, 1,2,4-triazole, benzotriazole, dimethyl malonate, diethyl malonate, diisopropylamine, dicyclohexylamine, N-tert-butyl-N-benzylamine, and c-caprolactam. 10 The polyurethane composition comprises as curing agent B a curing agent which comprises isocyanate-reactive groups and which is present in a blocked form, the blocking being possibly of chemical or physical nature. Examples of suitable chemically blocked curing agents 15 are polyamines attached to metals via a complex bond, more particularly complex compounds of methylenedianiline (MDA) and sodium chloride. Complex compounds of this kind are typically described by the empirical formula (MDA) 3 -NaCl. One suitable type is 20 available as a dispersion in diethylhexyl phthalate under the trade name Caytur@ 21 from Crompton Chemical. The complex decomposes on heating at 80-160 C with a rate which increases as the temperature goes up, releasing methylenedianiline as the active curing 25 agent. Examples of physically blocked curing agents are microencapsulated curing agents. Particularly suitable for use as curing agents in microencapsulated form are dihydric or polyhydric alcohols such as 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentyl glycol, diethylene 30 glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1,3- and 1, 4-cyclohexanedimethanol, hydrogenated 35 bisphenol A, dimeric fatty alcohols, 1,1,1 trimethylolethane, 1,1,1-trimethylolpropane, glycerol, pentaerythritol, sugar alcohols, low molecular mass alkoxylation products of the aforementioned dihydric WO 2008/077944 PCT/EP2007/064464 - 16 and polyhydric alcohols; short-chain polyester polyols such as bisglycol terephthalate; aliphatic, cycloaliphatic, and aromatic amino alcohols such as ethanolamine, propanolamine, butanolamine, 5 N-methylethanolamine, diethanolamine, triethanolamine; hydrazides of dicarboxylic acids; aliphatic polyamines such as ethylenediamine, 1,2- and 1,3-propanediamine, 2-methyl-1,2-propanediamine, 2,2-dimethyl-1,3-propane diamine, 1,3- and 1,4-butanediamine, 1,3- and 1,5 10 pentadiamine, 1,6-hexamethylenediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine and mixtures thereof, 1,7-heptanediamine, 1,8-octanediamine, 4-aminomethyl-1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12 15 dodecanediamine, methylbis(3-aminopropyl)amine, 1,5 diamino-2-methylpentane (MPMD), 1,3-diaminopentane (DAMP), 2,5-dimethyl-1,6-hexamethylenediamine, dimer fatty acid diamines; cycloaliphatic polyamines such as 1,2-, 1,3- and 1,4-diaminocyclohexane, bis(4-amino 20 cyclohexyl)methane, bis(4-amino-3-methylcyclohexyl) methane, bis(4-amino-3-ethylcyclohexyl)methane, bis(4 amino-3,5-dimethylcyclohexyl)methane, 1-amino-3 aminomethyl-3,5,5-trimethylcyclohexane (isophoronedi amine or IPDA), 2- and 4-methyl-1,3-diaminocyclohexane 25 and mixtures thereof, 1,3- and 1,4 bis(aminomethyl)cyclohexane, 1-cyclohexylamino-3 aminopropane, 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1] heptane (NBDA, produced by Mitsui Chemicals), 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0 2 6 ]decane, 30 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA), 3,9 bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3- and 1,4-xylylenediamine; aliphatic polyamines containing ether groups, such as bis(2-aminoethyl) ether, 4,7-dioxadecane-1,10-diamine, 4,9-dioxadodecane 35 1,12-diamine, and higher oligomers thereof, polyoxyalkylene-polyamines having theoretically two or three amino groups, available for example under the name Jeffamine@ (produced by Huntsman Chemicals); WO 2008/077944 PCT/EP2007/064464 - 17 aromatic polyamines such as methylenedianiline, diaminodiphenyl ether, diaminodiphenyl sulfone, the isomeric phenylenediamines, aminodiphenylamine. Preferred are the stated aliphatic, cycloaliphatic, and 5 aromatic polyamines. The microencapsulation of these curing agents may be carried out according to one of the common methods, as for example by means of spray drying, interfacial polymerization, coacervation, immersion methods or centrifuge methods, fluidized-bed 10 methods, vacuum encapsulation or electrostatic microencapsulation. The microcapsules thus obtained have a particle size of 0.1 to 100 micrometers, preferably 0.3 to 50 micrometers. The size of the microcapsules is made such that on the one hand they 15 open effectively on heating and on the other hand the adhesive after curing has an optimum homogeneity and hence cohesive strength. They must not, furthermore, exert any harmful influence on the adhesion properties of the adhesive. Suitable material for the capsule 20 shell includes polymers which are insoluble in the curing agent to be encapsulated and which have a melting point of 40 to 200 0 C. Examples of suitable polymers are hydrocarbon waxes, polyethylene waxes, wax esters, polyesters, polyamides, polyacrylates, 25 polymethacrylates or mixtures of two or more such polymers. In one preferred embodiment not only the polyurethane polymer containing isocyanate groups but also the curing agent are present in a blocked form in the 30 polyurethane composition. In a second embodiment the one-component reactive adhesive is a polyurethane composition comprising polyol and a blocked isocyanate curing agent dispersed 35 therein. This composition is characterized in that it comprises, as resin A that enters into polymerization reactions, a polyol or a mixture of polyols, and WO 2008/077944 PCT/EP2007/064464 - 18 comprises, as curing agent B containing isocyanate groups, an encapsulated isocyanate. In a third embodiment the one-component reactive 5 adhesive is an acrylate composition. This composition is characterized in that it comprises, as resin A that enters into polymerization reactions, at least one difunctional or polyfunctional monomer containing acrylic or methacrylic groups, and also at least one 10 monofunctional monomer containing acrylic or methacrylic groups. Examples of suitable difunctional or polyfunctional monomers containing acrylic or methacrylic groups are acrylates and methacrylates of aliphatic polyether polyurethanes and polyester 15 polyurethanes, polyethers, polyesters, novolaks, dihydric and polyhydric aliphatic, cycloaliphatic, and aromatic alcohols, glycols, and phenols. Examples of monofunctional monomers containing acrylic or methacrylic groups are methyl acrylate and 20 methacrylate, ethyl acrylate and methacrylate, hexyl acrylate and methacrylate, dodecyl acrylate and methacrylate, tetrahydrofuryl acrylate and methacrylate, and also hydroxyl-containing acrylates and methacrylates such as 2-hydroxyethyl acrylate and 25 methacrylate and 2-hydroxypropyl acrylate and methacrylate. As curing agent B the acrylate composition comprises a thermal initiator which is present in a blocked form and which initiates the polymerization of the acrylate 30 or methacrylate monomers. Examples of suitable thermal initiators are diacyl peroxides such as benzoyl peroxide, lauroyl peroxide, and decanoyl peroxide; peroxydicarbonates such as dipropyl peroxydicarbonate; peroxyoxalates such as di-tert-butyl peroxyoxalate; and 35 hyponitrites such as di-tert-butyl hyponitrite. Benzoyl peroxide is preferred. The blocked thermal initiator, more particularly benzoyl peroxide, is preferably in a microencapsulated form. The preparation of WO 2008/077944 PCT/EP2007/064464 - 19 microencapsulated organic peroxides is described in EP 0 730 493 B1, for example. In a fourth embodiment the one-component reactive 5 adhesive is an epoxide composition. This composition is characterized in that it comprises at least one polyepoxide as resin A that enters into polymerization reactions. Examples of suitable polyepoxides are diglycidyl ethers or polyglycidyl ethers of polyhydric 10 aliphatic, cycloaliphatic or aromatic alcohols, polyalkylene glycols, phenols such as bisphenol A, or of condensation products of phenols with formaldehyde which are obtained under acidic conditions, such as phenol novolaks and cresol novolaks; polyglycidyl 15 esters of polybasic carboxylic acids; and also N-glycidyl derivatives of amines, amides, and heterocyclic nitrogen bases. Glycidylized novolaks, hydantoins, aminophenols, bisphenols or aromatic diamines are preferred. Also present are adducts of 20 liquid epoxy resins with reactive liquid rubbers. As curing agent B the epoxide composition comprises a curing agent which contains epoxide-reactive groups and is present in a blocked form or in crystalline form as a compound of low solubility in epoxides. Examples of 25 suitable curing agents are amines such as aliphatic, cycloaliphatic, aromatic or araliphatic, preferably primary or secondary, amines and polyamines; adducts and polyalkoxylation products of polyamines; amine terminated polyalkylene glycols; adducts of monophenols 30 or polyphenols with polyamides; polyamides, especially those deriving from aliphatic polyamines and dimerized or trimerized fatty acids; polysulfides; aniline formaldehydes; polyhydric phenols; polybasic carboxylic acids and their anhydrides. Preferred curing agents are 35 so-called latent curing agents such as dicyandiamides, urons, prepared by blocking isocyanates with amines, diurons, imidazoles, and combinations of these compounds with dicyandiamides.

WO 2008/077944 PCT/EP2007/064464 - 20 The one-component reactive adhesive further comprises at least one additive D. Suitable additives include, for example, the following auxiliaries and adjuvants: 5 Plasticizers, examples being esters of organic carboxylic acids or their anhydrides, phthalates, such as dioctyl phthalate or diisodecyl phthalate, adipates, such as dioctyl adipate, sebacates, organic phosphoric and sulfonic esters, polybutenes, and other compounds 10 that are nonreacting with isocyanates; reactive diluents and crosslinkers, examples being polyhydric alcohols, polyamines, polyaldimines, polyketimines or aliphatic isocyanates, such as 1,6-hexamethylene diisocyanate, 2,2,4- and 2,4,4-trimethyl-1,6 15 hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane 1,3- and 1,4-diisocyanate, and any desired mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclo hexane (isophorone diisocyanate or IPDI), perhydro 20 2,4'- and -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-tetramethylxylylene diisocyanate, isocyanurates of these isocyanates, oligomers and polymers of these isocyanates, and also their adducts with polyols; organic and inorganic fillers, such as ground or 25 precipitated calcium carbonates, which optionally are coated with stearates, especially finely divided coated calcium carbonate, carbon blacks, kaolins, aluminas, silicas, and PVC powders or hollow beads; fibers, of polyethylene, for example; pigments; catalysts for the 30 reaction of the isocyanate groups, examples being organotin compounds such as dibutyl tin diacetate, dibutyl tin dilaurate, dioctyl tin dicarboxylate, dibutyl tin dichloride, dibutyl tin diacetylacetonate, alkyltin thioesters, organobismuth compounds or bismuth 35 complexes, tertiary amines such as 2,2' dimorpholinodiethyl ether, for example; polyaldimines, polyketimines or polyoxazolidines; catalysts for the hydrolysis of aldimine, ketimine, and oxazolidine WO 2008/077944 PCT/EP2007/064464 - 21 groups, examples being organic carboxylic acids such as benzoic acid or salicylic acid, organic carboxylic anhydrides such as phthalic anhydride or hexahydrophthalic anhydride, silyl esters of organic 5 carboxylic acids, organic sulfonic acids such as p-toluenesulfonic acid or 4-dodecylbenzenesulfonic acid, or other organic or inorganic acids, or mixtures of the aforementioned acids; catalysts for the reaction of the epoxide groups, such as, for example, salicylic 10 acid, dicyandiamide, tertiary amines or quaternary ammonium compounds, Mannich bases, imidazoles, and also boron trifluoride or its complexes with organic compounds such as ethers and amines, where appropriate in blocked form; catalysts for accelerating the 15 acrylate polymerization, examples being tertiary amines such as N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethylbenzylamine, and N-alkylmorpholine, thioureas such as 1,3-diethylthiourea, or complexes or salts of nickel, cobalt, and copper, and also 20 combinations of these catalysts; rheology modifiers such as, for example, thickeners or thixotropic agents, examples being urea compounds, polyamide waxes, bentonites or fumed silicas; adhesion promoters, more particularly silanes such as alkylsilanes, 25 epoxyalkylsilanes, vinylsilanes, aldiminoalkylsilanes, methacryloyloxyalkylsilanes, and isocyanatoalkyl silanes, and also oligomeric forms of these silanes; waxes; driers, examples being p-tosyl isocyanate and other reactive isocyanates, orthoformic esters, calcium 30 oxide or molecular sieves; stabilizers against heat, light, and UV radiation; flame retardants; surface active substances, examples being wetting agents, flow control agents, deaerating agents or defoamers; fungicides or fungal growth inhibitor substances; and 35 also further substances typically used in reactive adhesives. It is clear to a person skilled in the art which auxiliaries and adjuvants are suitable for the particular embodiment of the reactive adhesive.

WO 2008/077944 PCT/EP2007/064464 - 22 One-component adhesives of this kind are easy to use. In view of the blocking of resin and/or curing agent, they are extremely stable on storage. In the preferred 5 embodiments, given the blocking of resin A and/or curing agent B, they are not susceptible to moisture. They have good mechanical properties, and these properties can be adjusted within a wide range. 10 Examples of reactive adhesives: two-component systems In the case of two-component systems it is necessary for one component to be stored separately from the other, and to be released in a targeted way on 15 application. The reactive adhesive is composed in this case of a resin and a curing agent. A viscosity < 7000 mPa-s is necessary for thorough mixing of the components. The viscosity can be adjusted 20 by an increase in temperature. This increase in temperature may occur as a result, for example, of introduction of microwaves or by induction; the absorption of energy may be improved by means of absorbing particles in the adhesive formulation, such 25 as electrically conducting particles or nanoscale or microscale ferrites, as also described above in the examples of the one-component systems. The storage-stable reactive adhesives present as 30 separate components may be based, for example, on the following systems: 1) Epoxy resins and curing agents 35 As epoxy resin it is possible here to use any desired epoxy resins; the epoxy resin preferably contains at least two epoxide groups in the molecule. Suitable epoxy resins are more particularly those having more WO 2008/077944 PCT/EP2007/064464 - 23 than one epoxide group, p-methylglycidyl group or 2,3-epoxycyclopentyl group, which are attached to a heteroatom, such as sulfur, for example, but preferably to oxygen or nitrogen, more particularly bis(2,3 5 epoxycyclopentyl) ether, diglycidyl ethers or polyglycidyl ethers of polyhydric aliphatic or aromatic alcohols such as butane-1,4-diol, or polyalkylene glycols such as polypropylene glycol; diglycidyl ethers or poly9lycidyl ethers of cycloaliphatic polyols such 10 as 2,2-bis(4-hydroxycyclohexyl)propane; diglycidyl ethers or polyglycidyl ethers of polyhydric phenols such as resorcinol, bis(p-hydroxyphenyl)methane, 2,2-bis(p-hydroxyphenyl)propane (bisphenol A), 2,2-bis (4'-hydroxy-3',5'-dibromophenyl)propane, and 1,1,2,2 15 tetrakis(p-hydroxyphenyl)ethane, or of condensation products of phenols with formaldehyde which are obtained under acidic conditions, such as phenol novolaks and cresol novolaks, and also the di(B methylglycidyl) ethers or poly(-methylglycidyl) ethers 20 of the aforementioned polyhydric alcohols or phenols. Additionally suitable are polyglycidyl esters of polybasic carboxylic acids such as phthalic acid, terephthalic acid, tetrahydrophthalic acid, and hexahydrophthalic acid, the N-glycidyl derivatives of 25 amines, amides, and heterocyclic nitrogen bases such as N,N-diglycidylaniline, N,N-diglycidyltoluidine, N,N,O triglycidyl-p-aminophenol, N,N,N',N'-tetraglycidylbis (p-aminophenyl)methane, and triglycidyl isocyanurate. 30 Glycidylized novolaks, hydantoins, aminophenols, bisphenols or aromatic diamines are one preferred group of epoxy resins. Preferred compositions also comprise as resin a glycidylized cresol novolak, bisphenol A diglycidyl ether or a bisphenol A diglycidyl ether 35 which has been advanced using, for example, bisphenol A, dimeric fatty acids or a mixture thereof, and also mixtures thereof with aliphatic diglycidyl ethers.

WO 2008/077944 PCT/EP2007/064464 - 24 Possible epoxide curing agents are acidic or basic compounds. Examples of suitable curing agents are amines such as aliphatic, cycloaliphatic, aromatic or araliphatic, preferably primary or secondary, amines 5 such as, for example, ethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, triethylenetetramine, tetra ethylenepentamine, N,N-dimethylpropylene-1,3-diamine, N,N-diethylpropylene-1,3-diamine, 2,2-bis(4'-amino 10 cyclohexyl)propane, 3,5,5-trimethyl-3-(aminomethyl) cyclohexylamine (isophoronediamine), m-phenylene diamine, p-phenylenediamine, bis(4-aminophenyl)methane, bis(4-aminophenyl)sulfone, and m-xylylenediamine; adducts of polyalkylene-polyamines, such as 15 diethylenetriamine or triethylenetetramine, with acrylonitrile or monoepoxides such as ethylene oxide or propylene oxide, for example; amine-terminated polyalkylene glycols, available for example under the name JEFFAMINE@ (Huntsman); adducts of polyamines, such 20 as diethylenetriamine or triethylenetetramine, with polyepoxides, such as bisphenol A diglycidyl ether, prepared with an excess of these polyamines; adducts of monophenols or polyphenols with polyamides; polyamides, especially those deriving from aliphatic polyamines 25 such as diethylenetriamine or triethylenetetramine, for example, and dimerized or trimerized fatty acids (e.g., Versamide@ of dimerized linoleic acid); polysulfides, obtainable for example under the name THIOKOL®; aniline-formaldehydes; polyhydric phenols, examples 30 being resorcinol, 2,2-bis(4-hydroxyphenyl)propane or phenol-formaldehyde resins (novolaks); polybasic carboxylic acids and their anhydrides, such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydro phthalic anhydride, 4-methylhexahydrophthalic 35 anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, 4-methyl-3,6-endomethylene-4-tetrahydro phthalic anhydride (methylnadic anhydride), succinic anhydride, adipic anhydride, trimethyladipic anhydride, WO 2008/077944 PCT/EP2007/064464 - 25 sebacic anhydride, maleic anhydride, dodecylsuccinic anhydride, pyromellitic dianhydride, trimellitic anhydride, benzophenonetetracarboxylic dianhydride, or mixtures of anhydrides. Amines and polyaminoamides are 5 preferred curing agents. The composition may also comprise accelerators or curing catalysts. Examples are as follows: tertiary amines or quaternary ammonium compounds, Mannich bases 10 such as 2,4, 6-tris (d-imethylaminomethyl)phenol, benzyl dimethylamine, 2-ethyl-4-methylimidazole, monophenols or polyphenols such as phenol and bisphenol A, salicylic acid, dicyandiamide, boron trifluoride and its complexes with organic compounds such as ethers and 15 amines, examples being BF 3 -monoethylamine and BF 3 acetoacetanilide, phosphoric acid, and triphenyl phosphine. Tertiary amines, Mannich bases, and imidazoles are preferred. 20 The resin may further comprise tougheners, such as carboxyl-terminated polybutadienes, such as carboxyl terminated polybutadiene-acrylonitrile copolymers, reactive liquid rubbers, prepared by reacting polyether diol isocyanates with diphenols or hydroxy-epoxide 25 compounds, or core shell particles, and also thixotropic agents, based for example on a urea derivative in a nondiffusing carrier material. Advantageously this thixotropic agent comprises a blocked polyurethane prepolymer as carrier material. 30 The preparation of such urea derivatives and carrier materials is described in detail in EP 1 152 019 Al. 2) Polyisocyanates and polyol or polyamine curing agents 35 Suitable systems are for example: - Polyoxyalkylene polyols, also called polyether polyols, which are the polymerization product of WO 2008/077944 PCT/EP2007/064464 - 26 ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3 butylene oxide, tetrahydrofuran or mixtures thereof, optionally polymerized by means of a starter molecule having two or three active hydrogen atoms such as, for 5 example, water or compounds having two or three OH groups. Use may be made not only of polyoxyalkylene polyols which have a low degree of unsaturation (measured in accordance with ASTM D-2849-69 and expressed in milliequivalents of unsaturation per gram 10 of polyol (meq/g)), prepared for example with the aid of what are known as double metal cyanide complex catalysts (DMC catalysts), but also of polyoxyalkylene polyols having a high degree of unsaturation, prepared for example with the aid of anionic catalysts such as 15 NaOH, KOH or alkali metal alkoxides. Especially suitable are polyoxypropylene diols and triols having a degree of unsaturation of less than 0.02 meq/g and having a molecular weight in the range from 1000 to 30 000 g/mol, polyoxybutylene diols and 20 triols, polyoxypropylene diols and triols having a molecular weight of 400 to 8000 g/mol, and also what are called "EO-endcapped" (ethylene oxide-endcapped) polyoxypropylene diols or triols. The latter are special polyoxypropylene-polyoxyethylene polyols which 25 are obtained, for example, by alkoxylating pure polyoxypropylene polyols with ethylene oxide after the end of the polypropoxylation, and which consequently contain primary hydroxyl groups. - Polyhydroxy-terminated polybutadiene polyols, such 30 as, for example, those prepared by polymerizing 1,3 butadiene and allyl alcohol; - Styrene-acrylonitrile-grafted polyether polyols, of the kind supplied, for example, by Bayer under the name Lupranol; 35 - Polyhydroxy-terminated acrylonitrile/polybutadiene copolymers, of the kind preparable, for example, from carboxyl-terminated acrylonitrile/polybutadiene copolymers (available commercially under the name WO 2008/077944 PCT/EP2007/064464 - 27 Hycar@ CTBN from Hanse Chemie) and epoxides or from amino alcohols; - Polyester polyols, prepared, for example, from dihydric to trihydric alcohols such as, for example, 5 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol, glycerol, 1,1,1 trimethylolpropane or mixtures of the aforementioned alcohols with organic dicarboxylic acids or their 10 anhydrides or esters such as, for example, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, and hexahydrophthalic acid or mixtures of the 15 aforementioned acids, and also polyester polyols from lactones such as c-caprolactone, for example; - Polycarbonate polyols of the kind obtainable by reacting, for example, the abovementioned alcohols those used for constructing the polyester polyols 20 with dialkyl carbonates, diaryl carbonates or phosgene. The isocyanate-reactive polymers of difunctional or higher polyfunctional polyols having OH equivalent weights of 600 to 6000 g/OH equivalent, more 25 particularly of 600 to 4000 g/OH equivalent, preferably 700 to 2200 g/OH equivalent, are advantageous. Additionally advantageous are the polyols selected from the group consisting of polyethylene glycols, polypropylene glycols, polyethylene glycol 30 polypropylene glycol block copolymers, polybutylene glycols, hydroxyl-terminated polybutadienes, hydroxyl terminated polybutadiene-co-acrylonitriles, hydroxyl terminated synthetic rubbers, and mixtures of these stated polyols. 35 As isocyanate-reactive polymers it is also possible, furthermore, to use difunctional or higher polyfunctional amine-terminated polyethylene ethers, polypropylene ethers, polybutylene ethers, WO 2008/077944 PCT/EP2007/064464 - 28 polybutadienes, polybutadiene/acrylonitriles (e.g., Hycar@ CTBN from Hanse Chemie), and also further amine terminated synthetic rubbers or mixtures of the stated components. 5 It is additionally possible for isocyanate-reactive polymers to have been chain-extended as well, of the kind preparable in accordance with the person skilled in the art in a known way from the reaction of polyamines, polyols and polyisocyanates, more 10 particularly from diamines, diols and diisocyanates. Preferred isocyanate-reactive polymers are polyols having molecular weights between 600 and 6000 g/mol, selected from the group consisting of polyethylene glycols, polypropylene glycols, polyethylene glycol 15 polypropylene glycol block copolymers, polybutylene glycols, hydroxyl-terminated polybutadienes, hydroxyl terminated polybutadiene-acrylonitrile copolymers, and mixtures thereof. Particularly preferred isocyanate-reactive polymers are 20 a,c-polyalkylene glycols having C 2

-C

6 alkylene groups or having mixed C 2

-C

6 alkylene groups which are terminated with amino groups, thiol groups or, preferably, hydroxyl groups. Particular preference is given to polypropylene glycol and polybutylene glycol. 25 Suitable polyisocyanates are diisocyanates, triisocyanates or tetraisocyanates, especially diisocyanates or triisocyanates. Diisocyanates are preferred. Suitable diisocyanates are aliphatic, 30 cycloaliphatic, aromatic or araliphatic diisocyanates, especially commercial products such as methylenediphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), tolidine diisocyanate (TODI), isophorone diisocyanate 35 (IPDI), trimethylhexamethylene diisocyanate (TMDI), 2,5- or 2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane, 1,5-naphthalene diisocyanate (NDI), dicyclohexylmethyl diisocyanate (H 12 MDI), p-phenylene diisocyanate (PPDI), WO 2008/077944 PCT/EP2007/064464 - 29 m-tetramethylxylylene diisocyanate (TMXDI), and their dimers. Preference is given to HDI, IPDI, TMDI, MDI, and TDI. 5 Suitable triisocyanates are more particularly trimers or biurets of aliphatic, cycloaliphatic, aromatic or araliphatic diisocyanates, especially the isocyanurates and biurets of the diisocyanates described in the preceding paragraph. 10 Suitability is further possessed by surface-deactivated particles of solid polyisocyanates, of the kind described in R. Blum and H. Schupp, Progress in Organic Coatings (1990), pp. 275-288. 15 3) Acrylates and methacrylates and microencapsulated free-radical initiators Suitable systems are described in, for example, the 20 application WO 02/070620 Al and also the literature specified therein. They consist of methacrylic esters such as methyl methacrylate and tetrahydrofurfuryl methacrylate and also aliphatic polyurethane acrylates, elastomers reacted with acrylic acid, such as 25 polybutadiene-acrylonitrile copolymers (trade name HYCAR@ VTBNX) or core-shell polymers. Further suitable systems, composed essentially of mixtures of methacrylates with elastomers, are described in US 3,890,407, US 4,106,971, and US 4,263,419, for 30 example. Particularly suitable initiators are organic peroxides, especially benzoyl peroxide in combination with catalysts such as tertiary amines and/or complexes or salts of transition metals. Examples of tertiary amines are N,N-dimethylbenzylamine and N-alkyl 35 morpholine. Examples of complexes or salts of transition metals are complexes or salts of nickel, cobalt, and copper.

WO 2008/077944 PCT/EP2007/064464 - 30 The preparation of microencapsulated free-radical initiators such as peroxides are described for example in EP 0 730 493 Bl. 5 In figures 3A and 3B an inventive carrier element 2 is disposed in a column 21 of a vehicle body. The carrier element has channels 5 which can be filled with adhesive 4 via a filling opening 7. The channels 5 are outwardly open to the bodywork via openings 8 on the 10 surface of the carrier element, and so in these regions the adhesive 4 emerges from the carrier element 2. In these regions the adhesive fills out the cavity 16 between carrier element and bodywork, and so connects the carrier element to the bodywork. In the figures the 15 adhesive is shown only in the initial phase on emergence from the openings 8; if more adhesive is introduced, the adhesive becomes joined up to form a homogeneous area. In the end region of the carrier element 2 it is possible to dispose a seal 10. This 20 seal may be the carrier element itself, by virtue of said part being specifically shaped in this region, so that there is virtually no distance from the bodywork; it can be a seal of plastic of the kind typically used for sealing, such as, for example, an elastic material, 25 a strip of a foamable material, etc. By this means it is also possible for adhesives having a low viscosity to be used for bonding the carrier element in the body. Foamable materials which can be used are those described in connection with figure 1. 30 Figure 4 depicts a further inventive carrier element 2. In this embodiment the carrier element has channels 6 which are disposed on or in the region of the surface of the carrier element. These channels may have 35 different distances from the bodywork. Via a filling opening 9, which in this case is disposed in the bodywork in the region of the channels of the carrier element 2, it is possible for adhesive 4 to be filled WO 2008/077944 PCT/EP2007/064464 - 31 into the cavity 16 between bodywork and carrier element. The adhesive becomes distributed in the region of the channels 6 and in the regions which are at a distance from the bodywork. In the end region of the 5 carrier element 2 it is possible here as well to dispose a seal 11. This seal may be the carrier element itself, by virtue of said part being specifically shaped in this region, so that there is virtually no distance from the bodywork; it can be a seal of plastic 10 of the kind typically used for sealing, such as, for example, an elastic material, a strip of a foamable material, a puttylike material, etc. Puttylike materials used may be materials as described 15 above for the reactive adhesive, but also those which do not cure. The puttylike material is prepared preferably on the basis of polyurethane, epoxide, epoxide-polyurethane hybrid, synthetic rubber, PVC, etc., and is formulated so that it adheres well to 20 surfaces of plastic and also to surfaces of metal, especially to steel surfaces and to aluminum surfaces, which, moreover, may have been surface-treated. The puttylike material preferably adheres well to oiled steel, in order to prevent corrosion in the region 25 between steel and seal. Preferably, however, the puttylike material used is an adhesive as described above for the reactive adhesive. The material may have, moreover, a low expansivity of, for example, 10-100%, preferably 10-50%, in order to ensure correct extrusion 30 of the strand and sealing. It is also possible to use combinations of above-described foamable materials and puttylike materials. The material may be applied as a continuous strand by hand or in automated form by means of a robot. The 35 strand is preferably applied to the carrier element when the body is being assembled, shortly before the cavity is closed and the parts are welded. Alternatively the puttylike material may be applied to WO 2008/077944 PCT/EP2007/064464 - 32 the bodywork, i.e., for example, to the steel sheet, and the carrier element may only then be inserted. When the bodywork parts are joined, the strand is pressed between carrier element and bodywork and in this way 5 the seal is produced. The puttylike material may then cure in the subsequent operating steps as described below. The seal, however, is also obtained without curing of the puttylike material, and so the adhesive can be introduced into the cavity between bodywork and 10 carrier element even before the bodywork is coated, and the adhesive is cured in the baking operation for the coating. The puttylike material preferably has a low to moderate viscosity of 100-1500 Pas at a temperature of 40-60*C, in order to facilitate processing and to 15 ensure correct extrusion when the bodywork and the carrier element are assembled. At room temperature in the range of 10-300C, the viscosity ought preferably to be moderate to high and to be situated within a range of 500-5000 Pas. This is in order to obtain correct 20 sealing and to ensure that adhesive injected does not emerge through the seal or that the adhesive is not leached out when the bodywork is coated. In the baking operation for the coating of the bodywork, the puttylike material ought to retain its properties. 25 Foamable materials which can be used are those described in connection with figure 1. Depicted in the figure is a foamable material as seal 11. In the baking operation after coating of the bodywork, this material 30 forms a foam and seals off the interior space between carrier element and bodywork that is defined by the channels 6. As a result, adhesives with a low viscosity can also be used to bond the carrier element in the bodywork. In the bodywork it is possible for an exit 35 opening 12 to be disposed. This helps determine, in a simple way, when sufficient adhesive has been introduced into the interspace, by observation as to when adhesive emerges from the opening 12. This opening WO 2008/077944 PCT/EP2007/064464 - 33 12 is therefore disposed in the most remote region, which becomes filled with adhesive last. In the carrier element 2 it is also possible for there to be cavities 13 or passages, etc., disposed. These 5 regions are likewise sealed off by means of the seal 11, and so no adhesive can emerge in these regions. It is likewise possible for certain regions of the carrier element to be provided with a seal such that within these regions there is no adhesive present. In this way 10 it is possible to produce regions in which there is no connection between carrier element and bodywork, with the consequence that there is no reinforcement there. Figure 5 depicts in diagrammatic form the operation of 15 adhesive filling. The adhesive is introduced from an adhesive container 14 by means of a pump 15 and the fill opening 9 into the interspace 16 between carrier element and bodywork. 20 The method of installing the reinforcing element proceeds typically as follows. The carrier element is supplied to the site of production of the bodywork. The carrier element is inserted or placed into the cavity that is to be reinforced, this insertion or placement 25 taking place either by hand or by means of a robot. The carrier element is fixed in the cavity - this can be done arbitrarily, by means for example of mounting elements on the carrier element, mounting elements on the bodywork, adhesive, etc. The cavity is sealed if 30 necessary and the bodywork is welded or bonded or both. The body enters a deposition bath and is coated. This is followed by a baking operation for these coatings, and, if need be, foamable seals disposed on the carrier element foam up in the course of this operating step. 35 Thereafter, as described above, the adhesive is introduced into the cavity between bodywork and carrier element. This takes place, for example, via an opening 9 in the bodywork, directly via an opening 7, if need WO 2008/077944 PCT/EP2007/064464 - 34 be via a hose which is placed in the body and is connected to the opening 7. Correct filling with adhesive is monitored via an exit opening 12, and/or via the fill pressure, and/or via the fill volume. When 5 a particular fill volume of adhesive has been introduced, another material, air for example, or a material cheaper than the adhesive, can be introduced into the filling system in order to press the adhesive that has remained in the channels into the interspace 10 16 between carrier element and bodywork. By this means the channels are free from the adhesive, in order on the one hand to save on adhesive and on the other hand to allow subsequent filling. Depending on the design of the carrier element and/or of the channels, the flow of 15 adhesive can be adjusted so that, locally, more adhesive and hence better reinforcement takes place, according to where this is necessary. Alternatively the adhesive can be introduced before the 20 bodywork is coated. This allows the adhesion between carrier element and bodywork to be improved, since in this case bonding takes place not to the coating but instead directly to the bodywork. In that case, however, the carrier element must additionally have 25 outflow channels, to allow the coating material to flow through the carrier element in the coating operation. These outflow channels may be independent of the channels for introducing the adhesive. 30 The invention is, it will be appreciated, not confined to the working example described and shown. All cavity structures, i.e., all structural elements with cavities, can be reinforced using the systems described above. The channels on the support element are 35 arbitrarily exchangeable, i.e., it is also possible for channels in the support element to be mixed with channels on the support element.

WO 2008/077944 PCT/EP2007/064464 - 35 List of reference symbols 1 Reinforcing element 2 Carrier element 3 Distance 4 Adhesive 5 Channel 6 Channel 7 Filling opening 8 Exit opening 9 Filling opening 10 Seal 11 Seal 12 Exit opening 13 Cavity/passage 14 Adhesive container 15 Pump 16 Cavity/interspace 20 Reinforcing element 21 Vehicle structure/bodywork 22 Carrier element 23 Foamable material 24 Thickness unfoamed 25 Distance from bodywork 26 Thickness foamed

Claims (13)

1. A reinforcing system (1, 21) for reinforcing a cavity (16) of a structural element (21), a 5 carrier element (2) being connected to the structural element in the structural element for reinforcement purposes, characterized in that the support element (1) has channels 10 (5, 6), in that an adhesive is disposed in the cavity (16) between the carrier element (2) and the structural element (21), and in that the adhesive can be introduced into the cavity (16) between the support element and the structural 15 element by means of the channels (5, 6).

2. The reinforcing system of claim 1, characterized in that the channels (5, 6) are disposed in and/or on the support element. 20

3. The reinforcing system of claim 1 or 2, character ized in that at least one seal (10, 11) is disposed on the support element. 25

4. The reinforcing system of claim 1, 2 or 3, characterized in that on the structural element an opening (9) is arranged by means of which the adhesive can be introduced. 30

5. The reinforcing system of any of the preceding claims, characterized in that on the structural element an opening (12) is arranged by means of which the fill level of the adhesive can be read off. 35

6. The reinforcing system of any of the preceding claims, characterized in that the adhesive on curing exhibits an expansion of 0 to 5%. WO 2008/077944 PCT/EP2007/064464 - 37

7. The reinforcing system of any of the preceding claims, characterized in that the adhesive is a one-component reactive adhesive, more particularly 5 a polyurethane composition, a polyurethane composition comprising polyol and a blocked isocyanate curing agent dispersed therein, an acrylate composition, or an epoxide composition. 10

8. The reinforcing system of any of the preceding claims, characterized in that the adhesive is a two-component reactive adhesive, more particularly an epoxy resin and curing agent, a polyisocyanate and polyol or polyamine curing agent, or acrylate 15 and methacrylate and microencapsulated free radical initiators.

9. The reinforcing system of any of the preceding claims, characterized in that the structural 20 element is a vehicle structure.

10. A method of reinforcing a cavity (21) of a structural element, a carrier element (2) being connected to the structural element in the 25 structural element for reinforcement purposes, characterized in that the support element (1) is disposed in the structural element, in that the support element (1) has channels (5, 6) and adhesive is introduced 30 into the cavity (16) between the support element and the structural element by means of these channels (5, 6).

11. The method of claim 10, characterized in that the 35 adhesive is introduced before or after coating of the structural element. WO 2008/077944 PCT/EP2007/064464 - 38

12. The method of claim 10 or 11, characterized in that the fill level of the cavity between the support element and the structural element with adhesive is monitored by means of a special 5 opening and/or by means of the fill pressure of the adhesive and/or by means of the fill volume of the adhesive.

13. The method of claim 10, 11 or 12, characterized in 10 that adhesive disposed at least partly in the channels is expressed by means of air or by means of another material.